Unidades de Fluido Catalítico

3200 Fluid Catalytic Cracking Units
Author: R.S. (Scott) DuFault
Abstract
This section discusses the major corrosion and erosion problems in a fluid catalytic
cracking (FCC) unit. Included in this section are discussions on mechanism and
methods of control for: erosion, oxidation, hydrogen sulfide corrosion and cracking,
hydrogen damage, overhead stress corrosion cracking, and graphitization.
Contents Page
3210 Introduction 3200-2

3211 Process Description
3220 Catalyst Erosion 3200-5
3221 Mechanism of Catalyst Erosion
3230 Slide Valve Failures 3200-17
3240 Polythionic Acid SCC of Regenerator Internals 3200-21
3250 Oxidation and Graphitization 3200-21
3260 High Temperature Hydrogen Sulfide Corrosion 3200-23
3270 Low Temperature Hydrogen Sulfide Corrosion and Associated Hydrogen
Blistering 3200-24
3271 Fractionator Overhead Corrosion
3272 Fractionator Overhead Hydrogen Blistering and Wet H 2S Cracking
3273 Control of Hydrogen Sulfide Corrosion and Associated Blistering
3280 Sulfide Stress Cracking and Carbonate Stress Corrosion Cracking 3200-43
3290 References 3200-46
Chevron Corporation 3200-1 August 1999

3200 Fluid Catalytic Cracking Units Corrosion Prevention and Metallurgy Manual
3210 Introduction
Selection of materials for FCCs requires care to avoid serious corrosion and erosion
losses. There are areas where material performance can be improved. Changes in
materials will be made in future units as additional experience and more compre-
hensive knowledge of the problems make this possible. The seven problems of
greatest significance in materials selection are listed below with the equipment in
which they are likely to be encountered. Control measures most likely to reduce
their severity are also listed.
1. Catalyst Erosion
Location: Reactor and regenerator shells and internals, cyclone separators, catalyst
transfer lines, flue gas lines, fractionator side-cut and bottoms pumps, heat
exchangers, piping, catalyst slide valves, and catalyst line thermowells.
Control Method: Design to minimize turbulence of catalyst, use refractory linings
and hardfacing.
2. Regenerated Catalyst Slide Valve Failures
Location: Regenerated catalyst piping just below the reactor.
Control Method: Current state of the art is to replace stainless steel valves with
cold wall (refractory lined) carbon steel or low alloy steel valves. Chevron FCCs
are gradually changing to this type. For all valves, purging should be with nitrogen
rather than with steam.
3. Oxidation
Location: Regenerator and internals.
Control Method: Use a resistant alloy containing sufficient chromium or stainless
steel. Lower the shell temperature with refractory lining.
4. Hydrogen Sulfide Corrosion
High Temperature Sulfidation

Location: Reactor, reactor overhead line to main fractionator, flash zone and lower
section of fractionator.
Control Method: Use cladding or overlay having sufficient chromium (5% to 12%)
to resist attack. For hot wall reactors, use carbon steel or low chrome alloy with
adequate corrosion allowance or use cladding. An alternative for the reactor is cold
wall (refractory lined) carbon steel.
Aqueous Phase Corrosion

Location: Upper section of fractionator, fractionator overhead condenser and
piping, compressor intercooler and de-ethanizer feed cooler accumulators
and piping.
August 1999 3200-2 Chevron Corporation

Corrosion Prevention and Metallurgy Manual 3200 Fluid Catalytic Cracking Units
Control Method: Use proper inhibitors or ammonium polysulfide injection and

water wash at correct locations. On exchanger tubes, select the material best suited
to local conditions.
Hydrogen Damage (Blistering or Sulfide Stress Cracking)
Location: Fractionator overhead exchanger and accumulator, interstage accumu-
lator, HCN scrubber, compressor intercooler, stripper column, de-ethanizer, debuta-
nizer, and the associated depropanizer overhead equipment.
Control Method: Use water wash and ammonium polysulfide scrubbing to remove
HCN. Use lower strength bolting or stainless steel to avoid sulfide stress cracking.
Stress relieve carbon steel welds to avoid their stress corrosion cracking.
5. Carbonate Stress Corrosion Cracking (SCC)
Location: Fractionator overhead system, including accumulators, exchanger shells,
and associated piping up to the de-ethanizer and occasionally the de-ethanizer over-
head.
Control Method: Stress-relieve carbon steel or if cracking is severe, upgrade with
Type 304L stainless steel.
6. Graphitization
Location: Reactor, catalyst transfer line, and other locations operating at tempera-
tures between 825F and 1300F.
Control Method: Use chrome-molybdenum steels rather than the more commonly
used carbon and carbon-molybdenum steels. Insulating the ID with refractory may
lower metal temperatures, but inspection of the weld heat affected zones is still
recommended. For regenerator internals, use 300 series stainless steels.
3211 Process Description

The primary purpose of FCC is conversion of 600F1000F range distillates to
lower molecular weight products. Operating conditions and design are often varied
to maximize production of high octane gasoline, but the cracking process also yields
useful quantities of isobutane and light olefins suitable for alkylation and
polymerization.
The FCC process employs a catalyst in the form of very fine particles which behave
as a fluid when aerated with a vapor. This fluidized catalyst is circulated continu-
ously between the reaction zone and the regeneration zone. It acts as a vehicle to
transfer heat from the regenerator to the hydrocarbon feed and reactor, in addition to
promoting the cracking reactions.
There are two basic types of FCC units in use today:
The side-by-side type where the reactor and regenerator are separate vessels
adjacent to each other.
The stacked type where the reactor is mounted on top of the regenerator.

Several processes for fluid catalytic cracking are currently being licensed. Universal
Oil Products Company, M. W. Kellogg Company, Shell Development, Texaco,
Total, Stone and Webster, and Esso (Exxon) Research and Development have each
developed a cracking process which utilizes fluidized catalyst.
FCC units at Richmond, El Segundo, Hawaii, Salt Lake and Pascagoula were origi-
nally an Esso Model IV, but have been either partially or totally converted to a UOP
design. El Paso also had an Esso Model IV unit, which is now shut down. El Paso is
now operating a modern UOP designed unit that was formerly a part of El Paso
Refining. Burnaby also has a UOP licensed process. Corrosion problems are essen-
tially the same in all of the different configurations.
Reactor and Regenerator

In the Esso Model IV process, the reactor and regenerator vessels are mounted side
by side, connected by spent and regenerated catalyst transfer lines (U-bends) as
shown in Figure 3200-1. Conversion occurs in the reactor as the feed contacts a
catalyst. The catalyst is usually crystalline silica-alumina containing molecular
sieves (zeolites); average particle size is approximately 65 microns. Spent catalyst,
which is contaminated by coke, flows from the reactor through the spent catalyst
U-bend to the regenerator where the carbon is burned off. The regenerated catalyst
returns to the reactor through the regenerated catalyst U-bend.
The fluidized catalyst circulation rate depends on the unit heat balance and is
controlled by pressure balance and catalyst aeration rates. In configurations other
than the Model IV, circulation is controlled by slide valves in the catalyst transfer
lines. Catalyst circulation rates provide a complete turnover approximately every ten
minutes.
During the original FCC process, the catalyst and feed are mixed. The feed is vapor-
ized in the transfer line or riser and subjected to additional cracking in the riser.
CRTCs modified FCC process (based in part on Gulf Research and Development
Companys technology) increases the feeds temperature and residence time in the
riser. In this riser-cracking operating mode, the reactor is mainly a separator for
product and catalyst. Most of the cracking reaction occurs pre-reactor.
The following plants use the modified FCC process: El Paso (before it was shut
down), El Segundo, Pascagoula (before UOP modified it), and Richmond.
Fractionator Section
The cracked hydrocarbon gases leave the reactor through cyclones and pass to a
fractionator where light and heavy cycle oils are separated from the lighter frac-
tions. The overhead stream from the fractionator is piped to a gas recovery section
and subjected to fractionation, caustic treating and H2S removal. This yields gaso-
line and considerable quantities of propane, butane, and light gas. Heavy gasoline
(in some units) cycle oils are pulled as side cuts from the fractionator. The fraction-
ator bottoms product is a very heavy automatic oil that contains catalyst carried over
from the reactor.

Fig. 3200-1 Reactor Section of an ESSO Model IV Fluid Catalytic Cracking Process
Flue Gas Section

The flue gas section (for the regenerator gas) is similar for the Kellogg and Esso
Model IV processes. Flue gas from regeneration leaves the regenerator through
cyclone separators, which remove most of the entrained catalyst. In most units the
gas then passes through a steam generator and an electrostatic precipitator. Catalyst
particles too small to be separated by the cyclones are removed by the precipitator.
The flue gases either are discharged to the atmosphere or burned in a CO boiler for
further heat recovery.
3220 Catalyst Erosion

Erosion damage by catalyst has been the largest single problem in fluid catalytic
crackers. Although no portion of the reactor, regenerator and flue gas system is
immune to erosion, good design and material selection have reduced both its
severity and the frequency of failures. Erosion in Model IV crackers occurs prima-
rily in cyclones and the cyclone dipleg flapper or trickle valves; flue gas piping slide

valves and regenerated catalyst slide valves; thermowells, grid holes, around steam
injection piping in U-bends; and in fractionator bottoms and side-cut pumps, heat
exchangers, and piping. The serious nature of this erosion is evident in the photo-
graphs of catalyst damaged equipment, Figures 3200-2 through 3200-6.
3221 Mechanism of Catalyst Erosion

Our present knowledge of erosion and how to minimize it is based on experience,
rather than on a thorough understanding of the fundamentals involved. Catalyst
erosion can be described as a wasting action resulting both from particle impact and
cutting action. One notable characteristic is freedom of the fine particles to attack all
parts of an exposed surface. For example, a hardfacing alloy composed of hard
particles in a soft matrix will fail quickly when exposed to fluidized catalyst
because, as the soft matrix is eroded, the hard particles drop out.
Factors affecting erosion are separated into four general categories:
Properties of the catalyst
Operating conditions
Properties of materials
Equipment design
Properties of the Catalyst

The rate of erosion is affected by the hardness, size and shape of the catalyst
particles.
Operating Conditions
The exposure conditions known to affect rate of erosion are:
Particle concentration
Particle velocity
Angle of incidence
Temperature
Particle Concentration. Tests in FCC units have shown that erosion increases in
direct proportion to the particle concentration through the range found in the dilute
phase.
Velocity. Particle velocity strongly influences the rate of erosion. Erosion is usually
mild at 80100 ft/sec. Both theoretical calculations based on particle kinetic energy
and laboratory test data show that the erosion rate increases exponentially with
velocity to a power of between 3 and 4.
Angle of Incidence. Two types of erosion mechanisms operate as a function of
impingement angle as shown in Figure 3200-7. Brittle, high hardness materials are
eroded most rapidly at an impingement angle of 90 degrees, whereas the maximum
rate for relatively soft, ductile materials is at approximately 45 degrees [3]. In prac-
tice, turbulence probably causes both mechanisms to operate to some extent at all
angles. In FCC plants, we see maximum erosion at 30- to 50-degree incident angles.

Fig. 3200-2 Catalyst Erosion of Leg Supporting Vertical Baffle in a Regenerator. Baffle located between catalyst inlet
and overflow well. The seal between the base of the leg and the regenerator grid plate was imperfect,
permitting a stream of regenerating gases and catalyst to be directed along the base of the leg.

Fig. 3200-3 Eroded Catalyst Valve Slides. The flue gas line control valve slide in the upper photograph is carbon steel
and had been in service approximately 20 months. In the lower photograph the 4 inch valve slide from
first stage precipitator hopper is 12% chromium alloy hardened to Rc43. Erosion shown occurred in
approximately 8 months service.

Fig. 3200-4 Erosion of 12% Chromium Regenerator Seal, Refractory and Carbon Steel Shell (from leak in expansion
seal)

Fig. 3200-5 Erosion of Carbon Steel Case Liner, Fractionator Bottoms Pump. Case liner erosion due to high catalyst in
stock. Pump had been in service for 3 years. However, it does not run continuously.

Fig. 3200-6 Catalyst Erosion of 12 Cr Plug in Fractionator Bottoms Control Valve. Plug was coated with hard facing.
Valve began leaking after 4 to 5 months in service.
Temperature. Data relating the effect of temperature on catalyst erosion is some-

what sparse. Generally, temperatures in the 1100F to 1150F range (a typical
regenerator temperature before complete CO combustion) does not significantly
affect erosion rates. However, some Company units are now operating at 1300F
and above. In this temperature range, erosion rates may be accelerated by combined
actions of erosion and oxidation. Caution should be used when extrapolating low
temperature erosion data to high temperatures.
Properties of Materials
Erosion-Resistant Refractories. Refractory selection varies with locations within
the FCC, as well as among the many Company FCC units. Generally, erosion resis-
tance increases with increasing refractory density. Refractories are held in place by
hexmesh, s-bars, or anchors. Castable refractories are commonly reinforced with
stainless steel needles. For more detailed information on the types of refractories
used in a FCC unit, please refer to the Insulation and Refractories Manual.
Metallic Materials. Two materials of equal hardness may have greatly different
capacities to resist damage by catalysts. As already mentioned, erosion resistance
generally increases with hardness; however, there are several exceptions. Increased
hardness, achieved in a metal alloy by metallurgical modification (solid solution
hardening, precipitation hardening, cold work, or heat treatment) causes very little
change in its erosion resistance [2]. The hardness of carbon steel may be varied over
a wide range by heat treatment, but there is little change in its ability to resist
erosion [3].

Fig. 3200-7 Effect of Angle of Incidence of Catalyst Particles on Erosion Rate of Materials. Most materials
exhibit curves similar to one of the below. Ductile construction materials experience maximum erosion
at some angle less the 90, while brittle, high-hardness materials show a maximum rate of 90.
(Reprinted with permission of The American Ceramic Society, Westerville, Ohio. Copyright 1954. All
rights reserved.)
Several locations that have erosion problems cannot be covered with erosion-resis-
tant refractory. These locations require hardfacing for erosion resistance. Examples
of these locations are:
Flappers on trickle valves on the cyclone diplegs in both the reactor and
regenerator
Components of fractionator bottoms heat exchangers (such as channel baffles
and gasket surfaces)
Guides of the flue gas slide valves
Leading edge and guides of the regenerated catalyst slide valve
The grid on the bottom of the reactor [5]
Impellers and cases or liners of the fractionator bottoms pumps
Several hardfacing materials have been used in FCC units, and nearly all have been
applied using SMAW (stick) electrodes. McKay 100HC (chromium-iron base) hard-
facing has been used when available. It has a temperature rating up to approxi-
mately 900F. Stoody 2134 and Haynes 94 (both chromium-iron base hardfacings)
are more commonly used because of availability. These materials are rated to

approximately 1000F. For hotter locations, Stellite 6 (a cobalt-based hardfacing)

has been used up to 1500F [5].
In their January 1989 shutdown, Richmond installed four ceramic inserts in the
regenerator grid holes to determine catalyst erosion resistance. The ceramic inserts,
also known as air grid nozzles, are manufactured by Corhart. In 1991, the inserts
were found to have held up well, but the metal collars that held them in place were
near failure. The inserts were removed at that time.
On fractionator bottoms and side-cut pumps, the pump wear surfaces have been
eroded. At several Company locations, pump parts that cannot be hardfaced have
had an erosion resistant surface layer applied by vapor diffusion coating [1].
The relative erosion resistance of hardfacings to FCC catalyst has been evaluated in
Materials and Equipment Engineering tests [4]. The test results are presented in two
rankings, shown in Figures 3200-8 and 3200-9.
Figure 3200-8 shows hardfacing resistance ranking determined by penetration rate.
This ranking should be used for cases where very little loss in thickness during
service is tolerable. In this case, a hardfacing with low erosion loss should be
chosen, even if it is thin.
Figure 3200-9 ranks hardfacing resistance by time to penetrate the maximum thick-
ness of the hardfacing. This ranking should be used to maximize time before repair
in cases where some loss in thickness during service is acceptable.
The two rankings are different because the hardfacing thicknesses vary from 5 mils
to 190 mils. For both rankings, it is important to remember these are relative rank-
ings only. The penetration rates and times to penetrate through the hardfacing may
not reflect actual service performance and life [4].
Current practice is to use erosion-resistant refractory wherever possible. Metal hard-
facing is used where refractory will not do. In general, erosion resistance of refrac-
tory increases with density, while the erosion resistance of metallic materials
increases with hardness; however, exceptions exist.
For hardfacing design considerations for FCC catalyst erosion resistance, see
Figure 3200-10.
Feed Nozzle Erosion (Equipment Design)

Richmond, El Paso and El Segundo have used Sprayco nozzles in their feed system
[36]. Extensive testing at Richmond in 1984 showed substantial process gains and a
strong economic incentive to use the Sprayco nozzles [39]. However, erosion prob-
lems with the Sprayco nozzles limited their use.
The original Sprayco nozzle design used at Richmond damaged the feed riser as it
eroded [34]. The second generation designs were failsafe; that is, they did not
damage the feed riser as they eroded. They sustained process benefits for about 6 to
8 months, but after that they eroded to the point where they looked and performed
like a straight pipe nozzle.

Fig. 3200-8 Rank of Hardfacings and Steels by Penetration Rate. Relative ranking only. Do not assume penetration
rates will reflect those in actual service. (1 of 2)
Rank of Hardfacings and Steels by Penetration Rate (1)[4]
Manufacturer/Material Typ. Max. Pen. Rate,
/Substrate Hardness (2) Thick., mils in/yr Comments1
Steels:
T410 @ 1000F RB 100 5.2 1000F, 90 fps
T304 @ 1000F RB 85 5.3 1000F
T410 RB 100 5.5
Carbon steel (CS) RB 77 5.6
T410 RB 100 5.8 90 fps
T304 RB 85 6.4
1 Cr- Mo @ 1000F RB 88 6.6 1000F
1 Cr- Mo RB 88 12.2
CS @ 1000F RB 77 14.2 1000F
Hardfacings:
Union Carbide Knoop 950-1350 up to 17 0.4
LW5/CS
Watson Grinding 62 RC up to 25 0.5
83-17/CS
Sermatech Knoop 1000 up to 20 0.6
GG-WC-101/CS
Union Carbide RC 48-50 up to 17 0.9
LCIC/T304
Chromizing Knoop 1600-1900 45 0.9 1000F
Beta 5/T410 @ 1000F
Beta 5/T410 Knoop 1600-1900 45 1.2 90 fps
Beta 5C/T410 @ 1000F Knoop 1600-1900 45 1.2 1000F, 90 fps
Beta 5C/T410 Knoop 1600-1900 45 1.5 90 fps
Beta 5/T410 Knoop 1600-1900 45 1.7
Stellite RC 38-42 up to 190 1.8 1000F
6/CS @ 1000F
F. W. Gartner RC 65-68 up to 100 1.9
208/CS
Boroloy Knoop 2200 up to 30 1.9
C3/CS
Turbine Metals Tech. Knoop 1700-1900 45 2.0
56/5 Cr

Fig. 3200-8 Rank of Hardfacings and Steels by Penetration Rate. Relative ranking only. Do not assume penetration
rates will reflect those in actual service. (2 of 2)
Rank of Hardfacings and Steels by Penetration Rate (1)[4]
Manufacturer/Material Typ. Max. Pen. Rate,
/Substrate Hardness (2) Thick., mils in/yr Comments1
Turbine Metals Tech. Knoop 1700-1900 45 2.0 1000F
56/CS @ 1000F
Cermetco RC 69-70 up to 15 2.1
Metco 81VF-NS/CS
C1/CS
Stoody RC 55-60 up to 190 2.3 1000F
2134/CS @ 1000F
Turbine Metals Tech. Knoop 1700-1900 45 2.4
56/CS
C3/T410
C1/T410 Knoop 2050 up to 40 2.5
Stoody RC 55-60 up to 190 2.6
2134/CS
Turbine Metals Tech. Knoop 1700 45 2.6
601/T410
C1/T416
Chromizing Knoop 1600-1900 45 3.0
Beta 5C/T410
Stellite RC 38-42 up to 190 3.3
6/CS
C3/T416
Turbine Metals Tech. Knoop 1700 45 3.9
601/CS
F. W. Gartner RC 62-65 up to 35 4.8
600/CS
(1) Test run at ambient temperature and 120 fps, except as noted under comments.
(2) Note: RB100 RC23
RC70 Knoop 970

Fig. 3200-9 Rank of Hardfacings by Time to Penetrate Maximum Thickness. Relative ranking only. Do not assume
penetration rates will reflect those in actual service. (1 of 2)
Rank of Hardfacings by Time to Penetrate Maximum Thickness [4]
Typ. Max. Est. Time to Erode
Manufacturer/Material Generic Thickness, Penetration Through Max.
/Substrate Description mils Rate, in/yr Thickness, Days
Stellite Cr + W carbides in Co 190 1.8 40
6/CS/1000F
Stoody carbides in matrix 190 2.3 29
2134/Cs/1000F
2134/CS carbides in matrix 190 2.6 25
Stellite Cr + W carbides in 190 3.3 22
6/CS cobalt
83-17/CS 83% WC, 17% Co 25 0.5 18
F. W. Gartner Cr2O3, SiO2, TiO2 100 1.9 18
208/CS
LW-5/CS 68% W, 5% C, 22% Cr, 17 0.4 15
5% Ni
GG-WC-101/CS 85% WC, 15% Co 20 0.6 11
LCIC/T304 80% Cr3C2, (20% (80 17 0.9 7
Ni-20 Cr)
Boroloy B4C diffusion 30 1.9 7
C3/CS
C1/CS B6Si diffusion 40 2.2 7
C1/T410 B6Si diffusion 40 2.5 7
81 VF-NS/CS 75 CrC, 20 Ni, 5 Cr 15 2.1 4
Boroloy B4C diffusion 30 2.5 4
C3/T410
C1/T416 B6Si diffusion 40 2.9 4
C3/T416 B4C diffusion 40 3.4 3
Chromizing B diffusion 56 0.9 2.5
Beta 5/T410/1000F*
F. W. Gartner 98% Cr2, O3, 2SiO2 + 35 4.8 2.5
600/CS TiO2
Chromizing B diffusion 45 1.2 1.5
Beta 5/T410*
Beta 5C/T410/1000F* carburized + B 45 1.2 1.5
diffusion
Beta 5C/T410* carburized + B 45 1.5 1
diffusion

Fig. 3200-9 Rank of Hardfacings by Time to Penetrate Maximum Thickness. Relative ranking only. Do not assume
penetration rates will reflect those in actual service. (2 of 2)
Rank of Hardfacings by Time to Penetrate Maximum Thickness [4]
Typ. Max. Est. Time to Erode
Manufacturer/Material Generic Thickness, Penetration Through Max.
/Substrate Description mils Rate, in/yr Thickness, Days
Beta 5/T410 B diffusion 45 1.7 1
Turbine Metals Tech. carburized + B 45 2.0 1
56/5 Cr diffusion
56/CS/1000F carburized + B 45 2.0 1
diffusion
56/CS carburized + B 45 2.4 0.7
diffusion
T601/T410 B diffusion 45 2.6 0.7
Chromizing carburized + B 45 3.0 0.7
Beta 5C/T410 diffusion
Turbine Metals Tech. B diffusion 45 3.9 0.4
601/CS
Richmond developed radiography techniques for monitoring the condition of the

Sprayco nozzles on the run [40]. The periodic use of this technique was recom-
mended to ensure that the Sprayco nozzles did not damage the inside of the feed
riser, causing premature unit shutdowns, whenever the nozzles were used.
A third generation nozzle using a silicon nitride shroud was intended to avoid
damaging the feed riser and sustain process benefits by resisting erosion for the
entire run [35]. This design was first installed at El Paso in March 1985, and later in
El Segundo. These applications were unsuccessful. The nozzles failed from
mechanical damage to the ceramic shroud and external erosion of the OD metal
shroud [37, 38].
Currently Pascagoula, El Paso, and Richmond are using UOP-designed versions of
Sprayco nozzles. Their nozzles have all been in service about 8 years (as of 1999)
and no problems other than minor tip erosion at Pascagoula have been observed.
Burnaby has used Stone and Webster-designed atomizing nozzles for about 8 years
without problems. All other units are using straight pipe nozzles.
3230 Slide Valve Failures

Most refiners switched from low-alloy to stainless steel regenerated catalyst U-bend
slide valves in the 1970s when complete CO combustion raised regeneration
temperatures from 1100F to 1300+F. Company refineries have also made this
change. After several years of service, the industry observed several failures of the
stainless steel valves [12].

Chevron Corporation
Corrosion Prevention and Metallurgy Manual

Fig. 3200-10 Hardfacing Design Considerations for FCC Catalyst Erosion Resistance (1 of 2)
Mechanical Design Considerations
Typical Temp.
Manufacturer/ Generic Hardness, Thick., Application Limit Machinable? Field Line of Sight Substrate
Material Description Knoop Mils Method F Grindable? Applied? Limited? Alloys
Union Carbide 68W, 5C, 950-1350 to 17 D-Gun 1400 grindable No Yes all
LW5 22 Cr, 5 Ni <50-55 Rc
Union Carbide 80Cr3C2, 20 Rc 48-50 to 17 D-Gun 1800 grindable No Yes all

LC1C (80 Ni-20 Cr) <50-55 Rc
Watson Grinding 83 WC, Rc 62 to 25 Jetkote 1200 grindable No Yes all

83-17 17 Co <45 Rc
3200-18
Sermatech 85 WC, 1000 to 20 Gatorgard 1100 grindable No Yes all

GG-WC-101 15 Co
Chromizing B diffusion 1600-1900 4-5 CVD 1200 grindable No No Ferrous.

Beta 5 Beter on
T400 series
than T300

Chromizing carburized + 1600-1900 4-5 CVD 1200 grindable No No carbon, low-
Beta 5C B diff. alloy steels
F. W. Gartner CrO2, SiO2, Rc 65-68 to 100 Plasma 1000 grindable No Yes Ferrous, but
FWG 208 TiO2 not T416
(high S)
August 1999
F. W. Gartner 98 Cr2O3, 2 Rc 62-65 to 35 Rockide 1000 grindable Yes Yes Ferrous, but
FWG 600 SiO2 + TiO2 not T416
(high S)
Fig. 3200-10 Hardfacing Design Considerations for FCC Catalyst Erosion Resistance (2 of 2)
Chevron Corporation

Mechanical Design Considerations
Typical Temp.
Manufacturer/ Generic Hardness, Thick., Application Limit Machinable? Field Line of Sight Substrate
Material Description Knoop Mils Method F Grindable? Applied? Limited? Alloys
Boroloy B6 Si 2050 to 40 CVD 2075 grindable No No Ferrous,

C1 diffusion except T300
series. No
Ni alloys
Boroloy B4 C 2200 to 30 CVD 2075 grindable No No Ferrous,

C3 diffusion except T300
series. No
Ni alloys
Turbine Metals carburized + 1700-1900 4-5 CVD 1200 grindable No No Ferrous.

3200-19
Tech. B. diff. Better on

56 T400 series
than T300.
Turbine Metals B diffusion 1700 4-5 CVD 1200 grindable No No carbon, low-
Tech. alloy steels
601

Stoody carbides Rc 55-60 to 190 SMAW 1000 grindable Yes Yes carbon, low-
2134 / matrix alloy steels
August 1999
The industry has experienced problems with both cast and wrought valves. Cast
valves have cracked after becoming embrittled by sigma phase formation at service
temperatures above 1100F. Wrought valves have been cracked by polythionic acid
stress corrosion of sensitized stainless steel. Sensitization can occur during both
welding and service at temperatures above approximately 750F. Cast valves can
also sensitize in service, but they are not as susceptible to subsequent polythionic
acid stress corrosion cracking [8]. No Company FCCs use stainless slide valves
now.
Cast Stainless Steel

Four cast-stainless-steel failures were reported by the industry through 1983.
El Segundo had Company's only cast slide valve at that time. In light of the four
industry failures of cast slide valves, a sample from El Segundo's slide valve was
examined [8]. Metallographic examination showed no sigma formation, and only
8% ferrite. The Company's specifications require 8% maximum ferrite in austenitic
stainless steel castings to prevent sigma embrittlement in service above 1100F.
Industry experience indicates that ferrite content is dependent on section thickness,
so samples may not be representative of the entire casting. The metal temperature of
cast austenitic stainless steel must exceed 1100F for sigma embrittlement to occur.
In 1985, this slide valve cracked extensively from sigma embrittlement and was
replaced using a cold wall unit.
Wrought (Fabricated) Stainless Steel

Fifteen failures of wrought stainless steel slide valves were reported by the industry
through 1983, including Company failures at Irving and Richmond [6, 10]. Later,
El Paso and Salt Lake discovered that their wrought stainless steel regenerated cata-
lyst slide valves had cracked. All failures were by polythionic acid stress corrosion
cracking of sensitized Type 304H stainless steel. Cracking was attributed to the use
of wet purge steam and steam condensation that caused formation of the weak sulfur
acids needed for cracking. Several Company locations later used a nitrogen purge
rather than steam to minimize this problem.
Avoiding Slide Valve Problems

Actions necessary to prevent cracking vary for different types of slide valves, as
follows:
Cast Stainless Steel
Do not insulate. Insulation will allow the metal temperature to reach flue
gas temperatures, which are typically above 1100F, causing concern for
sigma embrittlement. Not insulating may result in distortion or sticking.
Keep temperature high enough to avoid condensation
Purge with nitrogen rather than steam.
Wrought Stainless Steel
Insulate and heat trace to prevent condensation
Purge with nitrogen rather than steam
Low-Alloy or Carbon Steel Valve
Line with refractory (cold wall). This is the best choice.

If a steam purge is used, intermittent rather than continuous purging is

recommended.
Purge with Nitrogen
Current practice is to continuously purge the stuffing box with a small
amount of nitrogen per the valve manufacturer's recommendations to keep
catalyst out of stuffing box. Nitrogen should be piped to the guide purges,
but these should only be used intermittently to help free the valve if it
sticks.
3240 Polythionic Acid SCC of Regenerator Internals

Catalyst is sometimes water washed from the regenerator to facilitate inspection.
Since sensitization of the 300-Series stainless steel may occur during service, poly-
thionic acid SCC is a concern when water is introduced into the regenerator.
Industry experience has been varied. Some plants have water washed without any
problems of cracking; other plants have used a soda ash solution to neutralize any
sulfur acids which may have formed by oxidation of iron sulfide deposits. Even
with a soda ash solution, cracking has occurred in some plants.
3250 Oxidation and Graphitization

Oxidation
One of the primary factors in selecting materials for use inside an FCC regenerator
is resistance to high temperature oxidation and sulfidation. Oxidation rates observed
in the regenerator are in good agreement with published high-temperature oxidation
rates. The sulfidation contribution is expected to be minimal in the regenerator.
A study [11] done in Company regenerators established several points concerning
high temperature oxidation:
At oxygen partial pressures greater than 0.02 psia (1 mm of Hg), the oxidation
rate of steel is nearly independent of oxygen partial pressure. Hence, oxidation
in FCC regenerators is the same as in air at similar temperatures.
Oxidation is based on a parabolic rate law, but because of spalling of the scale,
selection of oxidation resistant alloys should be based on the apparent one year
average oxidation rate [13].
The apparent one year average oxidation rate used for materials selection is
summarized in Figure 3200-11.
Graphitization
Graphitization is the formation of graphite by the decomposition of iron carbides in
carbon or carbon-molybdenum steels. It requires exposure to 825F1300F for
long periods and is most rapid around 1050F. Random nodular graphitization
generally does not significantly affect mechanical properties. More advanced chain
graphitization, which occurs preferentially in weld HAZ's, can lead to cracking.

Fig. 3200-11 Effect of Temperature on Oxidation Rate of Steels
Cracks occur when free graphite particles link together to form a continuous
graphite chain through the weld HAZ. Then, small loads or strains are able to pull
the graphite chain apart [30].
Susceptibility to graphitization is primarily dependent on exposure temperature,
time, and the steel making practice. Steels that are de-oxidized with aluminum are
more susceptible (such as ASTM A201 plate and ASTM A106 pipe). Steels such as
A53 pipe, A105 forgings, and A515 Grade 55 plate which are silicon-killed, are less
susceptible. Steels that are semi-killed and essentially not deoxidized, such as A285
plate, are least susceptible [31]. Avoiding aluminum-deoxidized steels which will
operate at temperatures above 825F has significantly decreased the graphitization
problem, but ambient temperature toughness of the steel can be a potential problem.
Silicon killed carbon steels are also preferred in FCC units because of their slightly
increased resistance to sulfidation corrosion, relative to carbon steels with low
silicon content.
The elements which improve graphitization resistance are carbide stabilizers such as
P, Mo, Mn and Cr. The elements which encourage graphitization are Si, Al, Ni, Co
and Cu.

Graphitization has not been a serious problem in Company FCC units, but it has
occurred. The most serious case was a weld crack in the spent catalyst transfer line
at Port Arthur [32]. Port Arthur used ultrasonic inspection to find locations which
were graphitized [33].
3260 High Temperature Hydrogen Sulfide Corrosion

Organic sulfur in the reactor feed may vary from 0.1 to 1.5 weight percent, and thus
the reactor effluent may contain up to 2 volume percent hydrogen sulfide. Conse-
quently, both high-temperature sulfidation and low-temperature aqueous sulfide
corrosion occur in FCC units.
High temperature hydrogen sulfide attack is a complex phenomenon which has been
studied intensively in the last decade. The environmental factors of prime impor-
tance are temperature and hydrogen sulfide concentration (which is a function of the
feed sulfur content). Temperature and velocity fluctuations may also influence
corrosion rate if fluctuations are sufficient to crack the protective iron sulfide
product scale.
High temperature sulfidation in fluid catalytic cracking plants is generally limited to
the reactor, reactor-to-fractionator line, and the lower section of the fractionation
column. Chrome additions are beneficial in reducing corrosion, and 12% Cr alloys
are virtually unaffected. However, carbon steel is an economical choice for much of
the equipment. In equipment other than the reactor, and the reactor-to-fractionator
line carbon steel's temperature threshold is approximately 550F-600F, and the
H2S concentration threshold is approximately 1 ppm. When carbon steel is used, the
Si content should be 0.10% minimum to take advantage of the slightly improved
sulfidation resistance. Applicable steels are ASTM A106 instead of ASTM 53.
When processing a representative feed with a total sulfur content of about 0.7 to
1.2 weight percent, carbon steel internals of the reactor typically corrode at rates
ranging from 5 to 15 mils per year. These rates are low enough to permit carbon
steel to be used for most internals (diplegs, cyclones, etc.) in the reactor. In cases
where the corrosion rates are too high to permit use of carbon steel, the reactor
internals have been upgraded to Type 410 stainless steel. The reactor and reactor-to-
fractionator line are typically constructed of a low-alloy (1- Cr - Mo) steel, and
high-temperature H2S corrosion has not been a problem.
Carbon steel corrosion specimens exposed in the bottom head of the main fraction-
ators have shown 6 to 19 mils per year corrosion rates, the highest rate being
observed at Richmond [12]. Typically, main fractionating columns are alloy clad
from the bottom head up to some intermediate level. Generally, the cladding is
12% Cr (Type 405 or 410S stainless steel), although some austenitic stainless steel
has occasionally been used. FCC corrosion rates as a function of H2S content and
temperature have not been well-established. Current practice has been to clad the
column where temperatures will exceed 600F. However, 575F may be a better
limit for the higher sulfur feedstocks (Arabian and Middle Eastern crudes) [12].
Consult a materials engineer for further information.

3270 Low Temperature Hydrogen Sulfide Corrosion and Associated

Hydrogen Blistering
Low temperature hydrogen sulfide corrosion occurs in the overhead of the fraction-
ator section. Hydrogen evolved by the corrosion process can cause blistering of the
steel.
3271 Fractionator Overhead Corrosion

Causes of Corrosion
Corrosion and blistering in the distillation and gas recovery section of FCC plants
are caused by the presence of:
A free water phase
High sulfide concentration
High ammonia concentration
High pH
Cyanides
The presence of these components leads to several corrosion mechanisms in the
overhead system, including:
Bisulfide corrosion of carbon steel
Wet H2S cracking and blistering of carbon steel
Ammonium bisulfide corrosion of carbon steel
Cyanide acceleration of all forms of damage to carbon steel
Ammonia corrosion of copper and copper alloys
Ammonia stress cracking corrosion of copper alloys
Water comes from steam injection into the reactor and fractionator, and from wash
streams injected to remove water soluble salts. Sulfide levels are often high in over-
head streams, and blistering and corrosion both increase with increased H2S in the
system.
Ammonia and cyanides are formed during the cracking process from nitrogen
present in the feed. As the nitrogen content in the feed increases, the ammonia and
cyanide contents in the overhead gas rise accordingly.
Large quantities of ammonia will increase the overhead water pH, which ranges
from 7.5 to 9.5 (typically 9.0 to 9.5 pH for most systems). Higher pH waters are
more corrosive, especially when cyanides are present. In addition to raising the pH,
higher ammonia levels increase the solubility of H2S. The increase in H2S solu-
bility makes more NH4HS (ammonium bisulfide) in the overhead water, which
attacks both carbon steel and copper alloys.
Ammonia complexes directly with, and aggressively attacks, copper alloys. Higher
pH will increase corrosion of admiralty even if no cyanides are present. This

increase in corrosion is especially likely in the intercoolers where the partial pres-
sure of NH3 is higher, so more NH3 dissolves.
The amount of cyanides generated in an FCC varies with feed rate and reactor
temperature. Reactor temperatures have increased historically, leading to higher
quantities of cyanide generated. Cyanides are particularly detrimental because they
increase the amount of atomic hydrogen that enters the steel, and therefore are
significant contributors to hydrogen blistering problems.
When cyanides are present, high pH water becomes much more corrosive to carbon
steel. Cyanides may complex directly with iron, or accelerate corrosion indirectly by
removing iron sulfide scales.
Overhead Hydrogen Sulfide Corrosion Mechanism

For process reasons, steam is added in the reactor and the fractionator, and water is
injected into the gas stream at several locations in the overhead. Although the liquid
water is removed by the knock-out system, the vapor is still water saturated. Where
water condenses, corrosion of exposed steel surfaces by aqueous hydrogen sulfide
can occur.
For FCC overhead systems within the 813 pH range, bisulfide (HS-) ions are the
predominant cathodic depolarizer [14, 15].
The anodic and cathodic reactions are thought to be:
Fe Fe++ + 2e- (anodic)

(Eq. 3200-1)
2HS- + 2e- 2H0 + 2S = (cathodic)

(Eq. 3200-2)
2H0 H2
(Eq. 3200-3)
The overall reaction is:
Fe + 2HS- FeS + S= + H2
(Eq. 3200-4)
When cyanide is not present, the FeS corrosion product is partially protective, and
corrosion rates drop with time. Cyanides accelerate the corrosion rates by removing
the protective FeS film. Cyanides (and sulfides) also interfere with the atomic-to-
molecular hydrogen reaction (Equation 3200-3), and corrosion-generated hydrogen
is more likely to cause blistering.

Heat Exchanger Corrosion Problems

A primary problem area in the overhead system has been H2S related corrosion and
blistering in the heat exchanger bundles and shells.
All plants except Hawaii which has generally run lower nitrogen feeds, have had
corrosion or blistering problems in the first stage compressor discharge coolers
(intercoolers). Problems in the overhead condensers and second stage discharge
coolers (aftercoolers) are less severe. Cooling water side corrosion problems have
also been prevalent in the FCC overhead system. Figure 3200-12 summarizes the
materials and corrosion concerns in a typical fractionator overhead system.
Chevron Experience with Heat Exchanger Hydrogen Sulfide Corrosion

Experience with tube materials has varied widely in the main fractionator overhead
condenser, the gas intercooler, and the aftercooler. Carbon steel is used where the
process and cooling water side corrosion can be controlled. When corrosion was a
problem (and the cooling water chlorides were less than 100 ppm), stainless steel
was the typical upgrade. Titanium has been used successfully to resist process and
cooling water side corrosion.
In the intercoolers, El Segundo currently has carbon steel exchanger bundles [20].
Richmond has admiralty; Pascagoula and Salt Lake have 304 stainless steel; El Paso
North had titanium for over 20 years. Port Arthur has successfully used stainless
steel (20 years) in the wet gas cooler (equivalent to the intercooler) of one FCC
unit and (galvanized) carbon steel in the other unit [24]. Hawaii has been most
successful with Admiralty bundles in intercooler service as shown in
Figure 3200-13.
In the aftercoolers, El Segundo uses carbon steel and El Paso North had titanium.
Richmond uses 304L; Salt Lake has carbon steel and 304L. Hawaii has admiralty.
Pascagoula installed a Saekaphen coated carbon steel bundle in 1986 [24], which is
performing acceptably (1998). Port Arthur has had mixed results with type
304 stainless steel. At one unit, Type 304 bundle lives have been over 25 years
while at another unit, 304 failed quickly from waterside chloride stress corrosion
cracking.
Figure 3200-14 details the distribution of overhead system exchanger bundle mate-
rials for six Chevron FCCs (1996).
It is difficult to set forth a coherent set of recommendations because process condi-
tions and cooling water quality vary significantly between refineries. Also, the fluc-
tuating cost of alloys such as titanium has a significant effect on the economics. As
bundle replacements become necessary, contact Materials Engineering at CRTC to
discuss options for optimum bundle materials.
The following discussion details company experience in three specific service areas:
overhead condensers, intercoolers, and aftercoolers.

Fig. 3200-12 Generic Fractionator Overhead System
Chevron Corporation

PASCAGOULA & EL PASO (N) ONLY
REFLUX
DRUM PASCAGOULA 304L NOTES:
140F BETWEEN ACCUMULATORS
FOR CARB. SCC 1. ALL EQUIPMENT CS EXCEPT
WHERE NOTED
CS, SOMETIMES UPGRADED TO
304SS CLAD SHELL FOR 2. STRESS RELIEVE ALL PIPING AND
VELOCITY ASSISTED VESSELS FOR CARBONATE STRESS
PROCESS CORROSION CRACKING RESISTANCE.
3. STRESS RELIEVE ALL VESSELS FOR

RESISTANCE TO WET H2S CRACKING;
UPGRADE WHERE APPROPRIATE
TO HIC-RESISTANT STEELS PER
LATEST MATERIALS ENGINEERING
GUIDELINES; 18-8 SS WELD OVERLAY
EL SEGUNDO: CLADDING FOR SEVERE CASES WHERE
304L FOR $36:$7(5,1-(&7,21 EXPERIENCE INDICATES.
CORROSION )25&25526,21
REFLUX DRUM &21752/ OVERHEAD CONDENSERS (CS SHELLS)

OR PRODUCT
ACCUMULATOR AFTER- ! HOT EXCHANGERS: ADMIRALTY AND Ti
TYPICAL; Ti WHERE NH3 SCC or NH4HS
3200-27
:$7(5_$36 (100F) COOLERS

,1-(&7,21
200220F CORROSION IS A CONCERN
)25+
! COLD EXCHANGERS: CS OR 18-8 IF CW

COMPATIBLE; ADMIRALTY IF NH3 SCC NOT A
%/,67(5,1*
CONCERN
+6&5$&.,1*
! Ti IF OTHER ALLOYS NOT SUITABLE
&21752/
INTERCOOLERS (CS SHELLS; SOME SS CLAD)
! Cu BASE ALLOYS SUSCEPTIBLE TO

PROCESS CORROSION
! 18-8 SS IF CW IS LOW Cl
AFTERCOOLERS

HCN SCRUBBER
WITH K.0. DRUM: ! Cu BASE ALLOYS SUSCEPTIBLE TO
EL SEGUNDO ONLY PROCESS CORROSION
! ID SAEKAPHEN-COATED CS FOR CW
COMPATIBILITY IF PROCESS CORROSION LOW
! 18-8 SS IF CW IS LOW Cl
RICHMOND:
304L FOR
CARB. SCC
August 1999
EL SEGUNDO:
316L FOR CARB. SCC
100F
Fig. 3200-13 Admiralty Intercooler Tube Life

25
Note: Each bar in the graph

20 represents a different data point for
Yrs Between Leaks of Retubes
the refinery. The bars do not

necessarily represent data points for
different equipment.
15
10
0
PASCAGOULA EL PASO HAWAII BURNABY SALT LAKE EL SEGUNDO RICHMOND
Fig. 3200-14 Current Tube Metal Distribution

Exchanger Tube Hottest Other
Material Totals Overheads Overheads Intercoolers Aftercoolers
Admiralty 20 6 8 3 3
Carbon Steel(1) 22 6 4 5 7
Titanium 14 8 6 0 0
304(L)SS 12 0 0 6 6
70/30 CuNi 3 1 1 1 0
316(L)SS 2 0 2 0 0
CS Saekaphen 1 0 0 0 1
Totals 74 21 21 15 17
(1) Includes air cooler tubes at El Paso South and Salt Lake.
Overhead Condensers
Materials Selection Recommendations for Overhead Condensers. Upgrade from
admiralty to 300 series stainless if cooling water parameters are within accepted
limits. Use titanium where ammonia SCC or NH4HS corrosion is a concern, and
where increased reliability and reduced fouling make titanium payout.
Stainless steel may be used where chloride levels in the cooling water permit.
Titanium tubes offer excellent resistance to both process side and cooling water
conditions.
The overheads can be divided into hot and cold service (or hot bank and cold bank).
Some FCCs, such as Pascagoula and El Paso North have two sets of overheads with
a reflux drum in between.

Hot Bank. In early years we used bimetallic tubes at Richmond and El Segundo
with mixed success. Some of the process side corrosion (on carbon steel) was prob-
ably due to ammonium chloride corrosion. Bimetallic tubes did not perform very
well, especially in the hot bundles. Bimetallic tubes are no longer generally avail-
able.
Other FCCs with admiralty had a reasonable life span for all the overheads due to
lower feed nitrogen content. As nitrogen levels rose, admiralty bundle lives
decreasedtubes failed from both ammonia corrosion and stress cracking. Type
70/30 copper-nickel provided cracking resistance and was better suited to high pH
corrosion, but less resistant to H2S corrosion.
Carbon steel is especially troublesome in the hotter exchangers where cooling water
corrosion is enhanced at the higher temperature.
Chevron then began using admiralty for the hotter bundles upstream of where water
condenses and forms ammonium bisulfide. Richmond moved their 300 series
bundles out of the hot bank when chloride levels went up in reclaimed water to
avoid cooling water side problems.
Admiralty in the hottest shells lasted generally about 1012 years and lasted
30 years at some locations. At Richmond, carbon steel lasted 68 years in the cooler
bundles.
Typical admiralty exchanger life averages 19 years at Hawaii, Port Arthur, Philadel-
phia, and Pascagoula Refineries. However, at Richmond, El Segundo, and El Paso,
where higher nitrogen feeds are processed, exchanger life with admiralty drops to a
69 year average.
El Segundo has seen severe plugging of intercoolers where cooling water leaked
into the system from overhead condenser leaks. El Segundo monitors calcium in the
V700 overhead drain sour water to detect this. The use of titanium bundles in the
overhead appears to have eliminated this problem.
Cold Bank. Several plants also use admiralty brass in the colder bundles, but again
with mixed results. Carbon steel was used in the colder overhead condensers at
Richmond and El Segundo because of NH3 stress corrosion cracking of admiralty
brass tubes. Stainless steel has been used where chloride levels in the cooling water
permit.
Stainless steel is acceptable if chlorides are low and velocities are sufficiently high
to prevent chloride pitting or corrosion. Type 300 series stainless can be used in the
colder bank if chlorides on cooling water side are less than about 50 ppm chlorides.
Richmonds upgrade to 304L proved satisfactory before the reclaimed water project
began.
El Segundo, El Paso, and Richmond have installed titanium, which has been
immune to the corrosives present. Titanium upgrades eliminate cooling water side
chloride concerns and ammonia attack of copper alloys. Titanium is the best choice
to resist process side contaminants and cooling water. However, titanium is expen-
sive and susceptible to hydriding if your mean temperatures are above 180 F.

Titanium tubes offer excellent resistance to both process side and cooling water
conditions. El Paso North has replaced all four of their bundles (hot and cold) with
titanium after 3 of their 4 admiralty brass bundles failed in 5 years. El Segundo
replaced their admiralty brass bundles with titanium due to severe shell side fouling.
The shell side fouling was caused by corrosion products (CuS and ZnS) and by tube
side cooling water leaks.
Intercoolers and Aftercoolers

Intercoolers. The same general guidelines and comments on overhead bundles
apply to intercoolers. However, because the partial pressure of ammonia and
hydrogen sulfide are higher downstream of the compressor, these contaminants are
forced into the water phase. Ammonium bisulfide corrosion has historically been
more pronounced herecausing localized corrosion and wet H2S cracking of
carbon steel at Richmond, El Segundo, and El Paso North.
The process side problems with admiralty are most pronounced in the intercooler
service. Copper alloys do not fare well in this service when feed nitrogen levels are
above about 1000 ppmw. Various refineries that no longer use admiralty in this
service include Pascagoula, Port Arthur 1241 and 1242, El Segundo, and Philadel-
phia. El Paso North installed admiralty coupons in the intercoolers; the coupons
corroded at 24 and 38 mpy. One of the admiralty intercoolers installed at Richmond
in 1995 failed after 15 months.
A 1988 Company survey found that only Hawaii had any success with admiralty
brass tubes in intercoolers (see Figure 3200-13). However, Hawaii processed a low
nitrogen feed (< 2,000 ppm wt) and maintained a lower pH (8.0) than other units in
overhead water draws. Most other units have higher pH (8.59.5) water draws and
have had poor life with copper-based alloys. Since the 1988 survey, Hawaii has
experienced stress corrosion cracking failures of admiralty brass bundles when
processing high-nitrogen Alaska North Slope crudes. Cu-Ni intercoolers tubes at
Hawaii failed because of ammonium bisulfide corrosion after 5 years.
Aftercoolers. Tube materials for aftercoolers are similar to those for intercoolers,
except that in most cases the aftercooler environment is not quite as severe since
much of the corrosive contaminants have already been washed out. In Chevrons six
active FCCs, half of the bundles are carbon steel, the remaining units are 300 series
stainless steel or admiralty. Carbon steel or 304 stainless can be used if compatible
with cooling water. Pascagoula has a Saekaphen coated carbon steel bundle.
Saekaphen coating the tube IDs is one way around the carbon steel/cooling water
corrosion problem, but the integrity of the coating is critical.
Materials Selection for Intercoolers and Aftercoolers. Use carbon steel where
process corrosion is low and compatible with cooling water, although it may be
subject to ammonium bisulfide corrosion. Ammonium polysulfide (APS) injection
ahead of a carbon steel intercooler should extend carbon steel life.
Admiralty brass is sometimes acceptable, but it usually has a high pH corrosion
concern. Admiralty has had spotty performance history.

Use 304 stainless where cooling water chlorides are low (less than about
400 ppm wt). Avoid throttling cooling water flow to achieve temperature. Low flow
rates make cooling water problems worse.
Titanium has excellent resistance to process side and cooling water corrosion and
has proven its success at El Paso.
Figure 3200-15 details the current metallurgy for several Chevron FCCs.
3272 Fractionator Overhead Hydrogen Blistering and Wet H2S Cracking

Equipment Susceptible to Hydrogen Blistering
All the refineries that had blistering experienced it on the intercooler shells. Only
Richmond and El Segundo reported blistering between 1972 and 1980. At Rich-
mond, it occurred in one particular plate of a heat exchanger shell, indicating the
importance of steel cleanliness. Blistering has also been observed on floating head
covers, baffles, gate valves, and column internals. Pascagoula eventually replaced
their de-ethanizer due to blistering. El Paso Norths deethanizer column experi-
enced wet H2S cracking and blistering in the top half.
Equipment Susceptible to Wet H2S Cracking

Generally, the same equipment subject to blistering is also susceptible to wet H2S
cracking.
Results from Chevrons Wet H2S special inspection program indicate the extent of
this cracking problem in our FCCs. Figure 3200-16 summarizes the results of the
inspection program, as of August 1998.
Hydrogen Blistering and Wet H2S Cracking Mechanism

Section 451 of the Corrosion Prevention and Metallurgy Manual discusses the
mechanism of hydrogen blistering. Section 452 reviews the mechanisms for HIC
and SOHIC forms of wet H2S cracking in extensive detail.
Materials Selection to Reduce Hydrogen Blistering and Wet H2S Cracking

The susceptibility of carbon steel to blistering is directly related to internal dirt or
voids in the steel. Defects such as porosity, nonmetallic inclusions and laminations
are largely a function of steel mill practice. Follow current company guidelines for
steel selection and fabrication when replacing heat exchanger channels and shells,
and vessels or columns in the overhead system. These guidelines include specifica-
tions for special steel chemistry, fabrication requirements and supplemental testing
and inspection. See Corrosion Prevention and Metallurgy Manual Section 457 for
additional information.

Fig. 3200-15 Current and Past Metallurgy of FCC Bundles
Chevron Corporation

Richmond (pre-Mod) Richmond (post-Mod.) El Segundo Pascagoula Salt Lake FCC
Location: Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy
Hot Overheads E-100-A Admiralty E-100-A Titanium-2 (u-tube) E-100-A Titanium E-1606-A Admiralty E-201-A Admiralty
Hot Overheads E-100-C 316 S/S (u-tube) E-100-C Titanium-2 (u-tube) E-100-C Titanium E-1606-C Admiralty
Hot Overheads E-100-E 316 S/S (u-tube) E-100-E Titanium-2 (u-tube) E-100-E Titanium E-1606-B Admiralty
Hot Overheads E-100-G Admiralty E-100-G Admiralty E-100-G Titanium E-1606-D Admiralty
Hot Overheads
Hot Overheads
Cold Overheads E-100-B Carbon Steel E-100-B Titanium-2 (u-tube) E-100-B Titanium E-201-B Admiralty
Cold Overheads E-100-D Carbon Steel E-100-D Titanium-2 (u-tube) E-100-D Titanium
Cold Overheads E-100-F Carbon Steel E-100-F 316 E-100-F Titanium
Cold Overheads E-100-H Carbon Steel E-100-H 316 E-100-H Titanium
Cold Overheads
Cold Overheads
3200-32
2nd Bank Cold O/H (warm) E-100-J Admiralty E-1607-A Admiralty

3rd Bank Cold O/H (warm) E-100-K Admiralty E-1607-C Admiralty
2nd Bank Cold O/H (cool) E-1607-B Admiralty
2nd Bank Cold O/H (cool) E-1607-D Admiralty
Intercoolers (warm) E-140-A 304 S/S E-133-A Admiralty E-140-A Carbon Steel E-1616-A 304L S/S E-241 a/c Carbon Steel
Intercoolers (warm) E-140-C 304 S/S E-1616-C 304L S/S E-122 304 S/S

Intercoolers (cool) E-140-B 304 S/S E-133-B Admiralty E-140-B Carbon Steel E-1616-B 304L S/S E-222 304 S/S
Intercoolers (cool) E-140-D 304 S/S E-1616-D 304L S/S
Aftercoolers (warm) E-141-A 304 S/S E-148-A 304 L S/S E-141-A Carbon Steel E-1617 Saekephen/ E-132 304 S/S
CS
Aftercoolers (warm) E-141-C 304 S/S E-141-C Carbon Steel E-242 a/c Carbon Steel
Aftercoolers (warm) E-141-E Admiralty E-233 a/c Carbon Steel
Aftercoolers (mid.) E-141-B Carbon Steel E-148-B 304 L S/S E-123 304 S/S
August 1999
Aftercoolers (cool) E-141-D Carbon Steel E-148-C 304 L S/S E-141-B Carbon Steel E-223 304 S/S
Aftercoolers (cool) E-141-D Carbon Steel
Aftercoolers (cool) E-141-F Carbon Steel
Fig. 3200-16 Current and Past Metallurgy of FCC Bundles (2 of 3)
Chevron Corporation

El Paso South (ElP Ref) El Paso North Hawaii Port Arthur 1241 Port Arthur 1242
Location Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy Equip no. Metallurgy
Hot Overheads E-1300-A a/c Carbon Steel E-1901-A Titanium E-5330-A 70/30 Cu/Ni C-120-2A Admiralty C-109A Admiralty
Hot Overheads E-1300-B a/c Carbon Steel E-1901-C Titanium E-5330-C Titanium C-120-2B Admiralty C-109B Admiralty
Hot Overheads E-1300-C a/c Carbon Steel C-109-1A Admiralty
Hot Overheads E-1300-D a/c Carbon Steel C-109-1B Admiralty
Hot Overheads E-1300-E a/c Carbon Steel C-109-1C Admiralty
Hot Overheads E-1300-F a/c Carbon Steel C-109-1D Admiralty
Cold Overheads E-1302-A Carbon Steel E-1901-B Titanium E-5330-B 70/30 Cu/Ni C-109-2A Admiralty C-109C Admiralty
Cold Overheads E-1302-B Carbon Steel E-1901-D Titanium E-5330-D Admiralty C-109-2B Admiralty
Cold Overheads E-1302-C Carbon Steel C-109-2C Admiralty
Cold Overheads E-1302-D Carbon Steel C-109-2D Admiralty
Cold Overheads C-120-1A Admiralty
Cold Overheads C-120-1B Admiralty
3200-33
2nd Bank Cold O/H (warm) E-1902

3rd Bank Cold O/H (warm) E-1902-A
2nd Bank Cold O/H (cool) E-1902-B
2nd Bank Cold O/H (cool)
Intercoolers (warm) E-1315 a/c Carbon Steel E-1913-A Titanium E-5332-A Admiralty C-202 304 SS
Intercoolers (warm) C-201A 304 SS

Intercoolers (cool) E-1305 Carbon Steel E-1913-B Titanium E-5332-B 70/30 Cu/Ni C-201B 304 SS
Intercoolers (cool) C-222 ?
Aftercoolers (warm) E-1914 Titanium E-5403-A Admiralty C-304 Seacure Galvanized/

CS
Aftercoolers (warm) CS/
Saekaphen
Aftercoolers (warm)
August 1999
Aftercoolers (mid.) CS/

Saekaphen
Aftercoolers (cool) E-5403-B Admiralty Galvanized/
CS
Fig. 3200-16 Current and Past Metallurgy of FCC Bundles (3 of 3)
Chevron Corporation

Philadelphia 1232 Perth Amboy Burnaby Irving Oil
Location Equip no. Metallurgy Equip no. Metallurgy. Equip no. Metallurgy Equip no. Metallurgy
Hot Overheads C-109-A Admiralty 51 E-5-A Titanium E-5201 304 ss E-2531-A Admiralty
Hot Overheads C-109-C Admiralty 51 E-5-C 70/30 Cu/Ni E-2531-B Admiralty
Hot Overheads C-109-D Admiralty 51 E-5-E 70/30 Cu/Ni
Hot Overheads C-109-E Admiralty 51 E-5-G 70/30 Cu/Ni
Hot Overheads C-109-G Admiralty
Hot Overheads C-109-I Admiralty
Cold Overheads C-109-B Admiralty 51 E-5-B 70/30 Cu/Ni E-2503 Admiralty

Cold Overheads C-109-D Admiralty 51 E-5-D Titanium
Cold Overheads C-109-F Admiralty 51 E-5-F Titanium
Cold Overheads C-109-H Admiralty 51 E-5-H 70/30 Cu/Ni
Cold Overheads C-109-J Admiralty
Cold Overheads
3200-34
2nd Bank Cold O/H (warm)

3rd Bank Cold O/H (warm)
Intercoolers (warm) 53 E-1-A 70/30 Cu/Ni E-5202 316 ss E-2509 Admiralty

Intercoolers (warm) 53 E-1-C 70/30 Cu/Ni

Intercoolers (cool) 53 E-1-B 70/30 Cu/Ni
Intercoolers (cool) 53 E-1-D 70/30 Cu/Ni
Aftercoolers (warm) C-201A 53 E-2-A Titanium E-5203 304 ss E-2510 Carbon Steel
Aftercoolers (warm)
Aftercoolers (warm)
Aftercoolers (mid.) 53 E-2-B Titanium
August 1999
Aftercoolers (cool) C-201B 53 E-2-C Titanium

Fig. 3200-16 Wet H2S Cracking in Chevron FCCs

Chevron Inspection Results Per CRTC Wet H2S Cracking Database
Sorted from Highest to Lowest in Cracking Severity
% With Cracks Requiring % With Minor % With No

Vessel/Service # Inspected Weld Repair Cracking Cracks
Interstage KO Drum 9 56 33 11
Sponge Absorber 10 40 50 10
Interstage Cooler 6 33 33 34
Deethanizer 10 30 40 30
Depropanizer OVHD Cond. 10 30 40 30
Debutanizer Accumulator 8 25 63 12
Deethanizer Feed Cond. 8 25 25 50
Suction KO Drum 5 20 60 20
Fractionator (Top) 5 20 20 60
Frac. OVHD Reflux Drum 12 17 42 41
Deethanizer Feed Sep. 12 17 42 41
Frac. OVHD Cond. 51 14 22 64
Depropanizer Accumulator 12 8 33 59
Debutanizer OVHD Cond. 34 6 21 73
Depropanizer 8 0 75 25
Debutanizer 11 0 73 27
3273 Control of Hydrogen Sulfide Corrosion and Associated Blistering

At locations in the fractionator overhead system where water condenses, aqueous
hydrogen sulfide (H2S) corrosion occurs. This attack can be minimized by the
proper use of water wash and ammonium polysulfide (APS) injection, which
prevents substantial damage to compressor elements and to exchanger shells and
tubes [25].
Solving hydrogen blistering problems is best approached by decreasing the
hydrogen activity of the process. Like wet H2S attack, hydrogen blistering is also
controlled by water washing and APS to remove cyanides from the overhead. Since
a high pH promotes H2 attack, waterwashing is also beneficial because it dilutes
NH3, thus lowering the pH.
At the present time Pascagoula, Richmond, and El Segundo inject ammonium
polysulfide into recirculating sour water in the main fractionator overhead system.
Hawaii, Salt Lake, and El Paso South do not. Salt Lake injects Nalco filming amine
into the overhead exchangers; Hawaii injects Nalco oil soluble filmer into the over-
head condensers and intercoolers; El Paso South has injected Betz inhibitors into

their overhead condensers and intercoolers and is currently switching to NALCO

Chemicals. Burnaby also injects a corrosion inhibitor.
Water Washing
The reverse cascade (versus a parallel cascade) water injection system shown in
Figure 3200-17 is often used to achieve good water washing of the vapor stream
while reducing the amount of sour water produced. Unfortunately, the reverse
cascade water injection scheme also tends to concentrate the corrodents (NH3, H2S,
CO2, and HCN) in the lower pressure part of the overhead. Because of this higher
concentration of corrodents, polysulfide is normally used in conjunction with the
reverse cascade water wash system. If the reliability of the polysulfide system
cannot be assured, consider a parallel cascade water wash system, shown in
Figure 3200-18.
Fig. 3200-17 Typical Reverse Cascade System
Ammonium Polysulfide Injection

Refer to Section 500 for additional information on APS injection.
Continuing corrosion problems in first-stage gas-compressor discharge coolers
(intercoolers) at several Company FCC units led to special studies at Richmond and
El Segundo in 1972 [17]. During the period from 1976 to 1978, APS injection was
started at El Segundo, Richmond, Pascagoula and El Paso North. A Company-wide
questionnaire gathered data on operating and design variables in 1979 [14]. These
studies led to several conclusions regarding corrosion mechanisms and ways to

Fig. 3200-18 Typical Parallel Cascade System
minimize problems, including water wash, inhibitors, cyanide removal systems, and
different tube materials. This study also led to recommendations for ammonium
polysulfide (APS) injection into the fractionator overhead to convert harmful
cyanides to thiocyanates. A follow-up survey on APS effectiveness [18] indicates
that it has succeeded in decreasing fractionator overhead corrosion and H2 blis-
tering, and in increasing compressor reliability and exchanger life.
When the APS injection system operates properly, it is a very effective method of
decreasing corrosion and H2 blistering of carbon steel equipment. Overhead, inter-
cooler and aftercooler exchanger lives are increased and compressor reliability is
improved. In addition, it can often be economically justified by the decrease in sour
water produced and by savings on corrosion inhibitors.
Polysulfide Chemistry. Polysulfides mitigate corrosion or cracking in three ways:
Polysulfide reacts with cyanides to form harmless thiocyanates and thus
neutralize their damaging effects.
Polysulfide promotes the formation of a more adherent, protective sulfide scale,
converting FeS to FeS2.
Polysulfide inhibits the bisulfide reaction with iron.
Each of these functions is discussed in more detail in Section 600. Chevron strongly
prefers ammonium polysulfide (APS) over sodium polysulfide for FCC overhead

systems, because it is more reactive than sodium polysulfide, and because it simpli-
fies downstream water treating.
APS Injection Rates. The APS injection rate should be high enough so that the
water in the main accumulator is still rich in polysulfide. In systems where polysul-
fide-containing water flow is different from the standard reverse cascade flow, the
water in the last knock-out vessel before the water is excessed should still contain
polysulfide. The residual polysulfide should be controlled to 10 to 25 ppm. If
30 ppm or more is present, there may be enough sulfur in the sour water stripper
feed to cause column fouling and to give problems in effluent treating [24].
Calculating Amount of APS to Inject. There are three steps in determining the
correct amount of APS to inject:
1. determine the amount of cyanide produced
2. size the pump
3. use calculation method such as sample given in Section 633.
Step 1.
The first step in determining how much polysulfide to inject is to determine how
much cyanide is produced in the overhead (this is the hardest step, because
measuring cyanides is not always straightforward).
Chevrons approach is to inject enough polysulfide to combine with the
predicted amount of cyanide, plus the additional amount required to produce
1015 ppmw polysulfide in the sour water.
The measurement location for insuring residual polysulfide should be off the sepa-
rator that is the farthest wash water stream downstream from where the water is
injected. For example, if the wash water and polysulfide are injected into the inter-
stage separator and cascaded upstream to the fractionator overhead separator, then
the overhead separator water should be measured for residual polysulfide.
The amount of polysulfide injected should be measured using a reliable method
such as level glass drop, rotameters, pumpstroke, or prover gauge. A monthly check
of the usage rate should be made by measuring the change in inventory in the
storage tank, taking into account any deliveries that month.
The residual 1015 ppm of polysulfide is taken into account when sizing the
polysulfide injection pumps. The maximum recommended amount of polysulfide is
15 ppm. Past experience suggests that over 30 ppm residual polysulfide in the net
water may cause sour water stripper fouling.
Operators should be aware that feed changes can affect nitrogen levels, and
cyanides present, which can change the polysulfide demand.
A sample calculation for determining the theoretical amount of polysulfide required
for FCCs is given in Section 633 of the Corrosion Prevention and Metallurgy
Manual.

Step 2.
It is important to choose a pump with a wide capacity range (to deal with changing
refinery conditions), as well as one which can be used most frequently between
50% and 100% of capacity.
For a design capacity of 18 Gal of APS solution per day, choose a pump with a
maximum capacity of 18 2 = 36 gpd, so the pump operates at 50% of capacity.
However, if designing for twice the normal flow requires purchase of the next size
larger pump, consider dropping the maximum design flow to 133% of normal, so
the normal flow rate is 75% of capacity; this may allow for a smaller pump.
Potential Problems with APS Systems. The main problem with APS systems is
getting the chemical reliably into the overhead system. Low temperatures, exposure
to oxygen, and low pH (below 8.0) can cause the ammonium polysulfide chemical
to precipitate elemental sulfur, which can cause plugging of the injection equip-
ment. This often results in insufficient APS to protect the overhead system.
On pH, this must be checked at all points in the system. With FCC feed containing
little nitrogen or sulfur, the NH3 and H2S may condense out in the overhead and
intercooler systems, leaving mostly CO2 which depresses the pH in downstream
equipment. El Segundo recently experienced APS destabilization in C-145 cyanide
scrubber due to this phenomenon. The pH was acceptable in V-100, overhead accu-
mulator, marginal in V-140, interstage separator, but not acceptable in C-145.
Problems have also arisen because of improper pump sizing, unreliable pumps, and
improper injection locations [16, 18]. Here are two examples:
At El Segundo, an ineffective injection quill allowed polysulfide to impinge
directly onto a carbon steel pipe wall, resulting in a corrosion failure. A similar
problem occurred at El Paso North at the intercooler inlet piping.
In 1985 at Richmond the E-140 intercooler A shell was replaced because of
severe lake-type corrosion (150 mpy); the C shell was also corroded. The E-140
C shell had leaked through on the run. The wash water contributed to higher
velocities, and this made ammonium bisulfide corrosion worse.
Wherever APS is injected, it should be diluted with enough water so that no more
than 75% of the water vaporizes as it enters the process stream. Concentrated APS
solution will contribute to plugging and localized corrosion.
Alternatives to APS. Some Company locations use other types of corrosion inhibi-
tors to reduce corrosion in the overhead system. Filming amine inhibitors are used
currently at El Paso-South, Salt Lake, and Hawaii. Hawaii and Salt Lake use inhibi-
tors in part because the pH is too low for polysulfide. Neither plant has significant
corrosion problems, although more recently, Salt Lake has experienced significant
wet H2S cracking.
Naturally, chemical inhibitor companies such as Nalco, Betz, and Petrolite adver-
tise inhibitors for overhead systems that do not use APS.

Chevron has experimented with various inhibitors over the years. These inhibitors
generally have not been successful (or measurement of this effectiveness was incon-
clusive) at Richmond, El Segundo, and Pascagoula. Conventional wisdom is that oil
soluble amines are only effective at lower pH (47).
Although Nalco has claimed that its 165AC inhibitor effectively reduces corrosion
from H2S and cyanide in high pH streams, our experience does not support Nalcos
claim.
A reliable APS substitute does not appear to be available. Replacing APS with an
inhibitor would require economic justification, presumably based on a more reli-
able delivery system less susceptible to plugging, to offset higher raw material costs
and what we believe to be a less effective inhibitor in the vapor space.
Filming amine inhibitors are one class which has been used. These inhibitors work
by forming an amine film on the carbon steel equipment which acts as a barrier
between the steel and the corrosive stream.
If inhibitors other than polysulfide are used in FCC overhead systems, they should
be water soluble, or water dispersible, rather than oil soluble. This is because the
corrosive species exist in the aqueous part of the stream.
One key advantage we believe APS has over filming inhibitors is that it does a
better job protecting the vapor space of vessels and heat exchanger shells, because it
chemically removes free cyanide. Therefore, cyanide is not present in the water
droplets that condense in the vapor space of equipment.
The use of inhibitors for protection of admiralty brass tubes is not generally consid-
ered to be effective. Just as with APS, where inhibitors are being used, their effec-
tiveness should be monitored with hydrogen probes and corrosometers.
Recommended Practices. Figure 3200-19 summarizes Chevrons current thinking
about polysulfide injection systems. The figure covers injection locations, mechan-
ical aspects and system monitoring.
Fig. 3200-19 APS Recommended Practice Summary (1 of 3)

PRACTICE:
WHAT GI, GP, or BP* HOW
I. Type of Inhibition System GP Inject APS to control cyanide blistering and corrosion
in high nitrogen/high cyanide systems
II. Water Routing BP Parallel cascade for new system
III. Where to Inject
1. Overhead Condensers BP Inject ahead of second bank or second set of coolers
2. Intercoolers BP Inject ahead of hottest bundle(s)
3. Aftercoolers GP Inject ahead of hottest bundle(s)


PRACTICE:
IV. Water/APS Rates and Quill
1. Wash Water Rate BP Minimum 25% unvaporized
2. APS Rate BP 1015 ppm residual in sour water
3. Quill Design GP Drilled holes in closed-end quill
4. Quill Material GP 316L SS or better (e.g.Hastelloy C)
5. Other Quill Features GI Retractable
6. Mixing Distance GP Individual distributed locations to each heat exchanger
inlet nozzle
V. APS Pumps
1. Type GP Motor driven displacement pump
2. Brand /Model GP Milton Roy Simplex
3. Design Flow Rate GP Maximum output at operating pressure at 200% of
expected output, based on predicted lb/hr cyanide
4. No. of Pumps One pump per each APS injection location, plus one
spare
VI. Flow Meters for Water/APS
1. Type Any reliable flow meter
2. Meter Location and Number BP Individual meters to each injection branch
VII. APS Tank
1. Blanketing BP Nitrogen blanket, route vent to relief header for odor
control
2. Level Check Method BP Calibrated level gauge
3. Tank Size GI Use the smallest practical tank size so that inventory
turnover is high
VIII. APS System Monitoring
1. Color Test for APS in BP Check water in last drum in cascaded series for straw
Sour Water yellow color; use color standard in field
Frequency BP Once per shift
2. Cyanide Level Test Use spot test for ferrocyanide
Frequency Weekly
3. Lab Test for APS in Sour Water Use A-48 Method for APS in last drum in series
Frequency Only if you suspect you have problems
4. APS Tank Level Check Check calibrated level gauge
Frequency Weekly


PRACTICE:
5. Nitrogen Blanket Check Check for positive pressure
Frequency Daily
6. Sour Water pH Test Check sour water pH if feed nitrogen changes.
If pH drops below 8.5, stop APS injection and evaluate
options for raising pH to allow APS injection to
continue.
IX. Non-APS Inhibitor System Monitoring
1. Inhibitor Injection Rate Check gallon per day rate
Frequency Weekly
2. Residual Inhibitor Check for residual per vendor recommendations
Frequency Weekly
X. Hydrogen Probes
1. Locations BP The preferred location is always the vapor space of
Interstage KO drum
De-ethanizer column
De-ethanizer feed separator drum
2. Frequency measured Measure and record once per week; if activity noted,
check APS or inhibitor pumps and residual level in
sour water. Check for feed changes, or APS flow rate
changes
3. Probe Type Finger type pressure probe; Cosasco Model 6403 with
temperature gauge and 030 psi pressure gauge
XI. Bundle Metallurgy
1. Tube Materials Optimum metallurgy varies with operating conditions,
plant history, and cost of tubes; consult CRTC
2. Service Applications
Materials Engineering
* BP = Best Practice; GP = Good Practice; GI = Good Idea; ""= not categorized.
Hydrogen Monitoring for Blistering Susceptibility

The effectiveness of an APS and water wash system or a system using corrosion
inhibitors can be monitored using hydrogen probes. The probes indicate hydrogen
activity, which is an indication of the corrosivity of the stream. This is particularly
important where hydrogen blistering has been detected or is suspected.
Commercial probes are available and are generally adequate. As with any measure-
ment of corrosion, results must be interpreted carefully: a probe can indicate condi-
tions only in its immediate vicinity, and the conditions on the surface of the probe
may be different from those at the vessel wall. An inactive probe, therefore, does
not guarantee a lack of hydrogen damage to the vessel. However, if a probe shows

continued activity over a period of weeks, it is likely that the vessel itself is in
danger of blistering. Figure 3200-20 is a guide for interpreting increases in pressure
for pressure-type hydrogen probes.
Fig. 3200-20 Interpreting Pressure Increases for Hydrogen Probes

Minimal Some
Range of Acceptable Control Blistering Blistering Probable Severe Blistering
Hydrogen Activity(1) Range(2) Typicals Damage Expected Damage Expected
Range in psi/Day 01 1(3) >1 2550
Range in psi/Month 30 <5 530 > 30
(1) Monitoring frequency for finger probes is once/week.
(2) Activity is expected to be higher for first month after startup.
(3) This is about the minimum detectable rate for a finger probe.
Select probe locations carefully. Probes should be located where blistering has been
known to occur. In vessels where both liquid and vapor phases are present,
hydrogen attack may occur only in one phase and not the other. Thus, a probe may
be located where there is no hydrogen attack while blistering occurs a short distance
away. Place the probe in the vapor space instead of the liquid space wherever
possible.
Some recommended locations for installation of hydrogen probes are:
Interstage KO Drum
De-ethanizer Column near top head
Cyanide Scrubber top
Inlet or outlet of intercooler exchanger
Aftercooler inlet or outlet
Overhead accumulator
De-ethanizer Feed Separator
Sponge Column top
Section 400 of the Corrosion Prevention and Metallurgy Manual, and Reference
[46] discuss hydrogen probes in greater detail.
3280 Sulfide Stress Cracking and Carbonate Stress Corrosion Cracking

Sulfide Stress Cracking
Another form of hydrogen damage which can occur in high strength bolting and
valve trim in FCC gas recovery areas is embrittlement or sulfide stress cracking
(SSC). The general subject of hydrogen embrittlement (of which blistering and
cracking are two separate forms) is discussed in greater detail in Section 452 of the
Corrosion Prevention and Metallurgy Manual.

Sulfide cracking failures have been seen repeatedly in ASTM A-193, Grade B-7
floating head stud bolts in FCC overhead gas recovery exchangers. These bolts,
with 105 ksi minimum yield strength, are susceptible to cracking in aqueous H2S
environments. The use of ASTM A-193 Grade B-7M bolts which are heat treated to
below the 90 ksi yield strength threshold has solved this problem. (However, the
lower strength bolt must still be able to adequately seal the floating head.)
Other materials which have cracked in sour aqueous conditions include high-
strength 12 Cr valve trim and high-strength Bourdon tubes. High-strength materials
should be purchased in accordance with NACE MR-01-75, Standard Material
Requirements Sulfide Stress Cracking Resistant Materials for Oilfield
Equipment. [27]
Carbonate Stress Corrosion Cracking

Several Company refineries found extensive intergranular stress corrosion cracking
beginning in about 1985 in the following areas: nonstress-relieved carbon steel
welds, heat-affected zones (HAZ), and base metal in the fractionator overhead
condenser shells, accumulator vessels, and associated piping. This cracking has
been identified as carbonate SCC.
A 1989 test program to understand carbonate SCC used water samples taken
throughout the FCC overhead system at eight Chevron refineries [44]. The test
program showed that cracking correlated to water chemistry, open circuit potential,
and pH. Cracking is prevalent in systems having:
pH greater than 9 and carbonate ion concentration above 100 ppm.
pH between 8 and 9 and carbonate concentration above 400 ppm.
a susceptible electrochemical potential range between -500mv and -600mv
SCE.
These conditions often exist throughout the main fractionator overhead system, to
the first vessel in the gas recovery unit. We have found only very isolated instances
of carbonate cracking beyond the de-ethanizer.
Process variables have been identified which may directionally promote carbonate
stress corrosion cracking. Promoted catalysts encourage complete CO to CO2
combustion. This increases the amount of ammonium carbonate in the fractionator
overhead system.
An additional plant variable which appears to affect carbonate SCC is FCC feed
sulfur. Feed hydrotreating reduces FCC H2S make while CO2 remains the same.
Ammonia make typically does not drop as fast as H2S, since nitrogen is more diffi-
cult to remove from the feed than sulfur when hydrotreating. The use of APS adds
ammonia which raises the pH and may increase the risk of carbonate SCC.
Ammonium polysulfide helps to drive the electrochemical potential into the range
susceptible for cracking, which may explain why Chevron refineries experienced
more severe carbonate SCC than some others in the industry. However, our
successful experience with polysulfide in reducing hydrogen activity in the fraction-

ator overhead system and in the downstream Gas Recovery Unit and amine facili-
ties outweighs this consideration and makes its continued use beneficial.
Carbonate SCC is characterized by intergranular, somewhat branchy, scale-filled
cracks. It is believed that ammonium carbonate (NH4CO3) is the main contributor to
the cracking mechanism. The scale is typically a black magnetite (Fe3O4) corrosion
product and sometimes iron carbonate (FeCO3).This is unlike sulfide stress corro-
sion cracking, where the scale is iron sulfide.
Inspecting for Carbonate SCC. The preferred inspection technique is wet fluores-
cent magnetic particle and/or UT shear wave, depending on whether the equipment
can be internally inspected. Conventional UT shear wave inspection techniques are
successful at detecting whether cracks are present but fail to accurately measure the
depth of these branchy cracks. For crack sizing, more advanced UT methods are
needed. Current inspection recommendations are available from CRTC Materials
and Equipment Engineering. Radiography picks up only a small percentage of the
cracks, because the cracks are typically very tight.
To date, carbonate stress cracking has been found at Richmond, El Segundo,
El Paso North, Pascagoula, and Burnaby. Hawaii has had very little, and Salt Lake
and El Paso South have not had any.
Other FCC operators, including Exxon, Sohio, Caltex and Shell, have reported
similar intergranular SCC, which they believe is carbonate related. Carbonate SCC
of carbon steel has also occurred in coal gas plants and buried pipelines, and has
been reproduced in laboratory tests [42, 43].
Prevention Through Stress Relief. Stress relief is recommended to prevent
carbonate SCC of carbon steel. Carbonate SCC occurs on relatively soft (less than
Rc 22 hardness) carbon steel at stress levels above about 10 ksi. Use of a high
temperature (11501250F) stress relief procedure and limiting externally applied
stresses to 10 ksi will minimize occurrences of carbonate SCC in carbon steel.
Carbonate SCC is particularly troublesome because it requires only a small amount
of stress for cracking to occur. This makes the metal particularly sensitive to the
quality of stress relief. Stress relief practices that are satisfactory to prevent other
forms of stress corrosion cracking may not eliminate carbonate SCC. Pascagoula
developed a procedure for effective stress relief of piping welds [45]. A key element
is the width of the heated band and runout zone. Because cracks can grow at
improperly heat-treated welds or stressed areas in piping that are otherwise
satisfactory, continued inspection of installed piping is needed.
Prevention Through Materials Selection. In locations where cracking cannot be
tolerated, materials should be used which are immune to carbonate SCC. Such loca-
tions may include highly-stressed piping and equipment with high operating pres-
sures or changes in direction which create stress concentrations. Type 304L stainless
steel is currently the most economical material available which is believed to be
immune to carbonate SCC. Consider using 300 series stainless steel at pump inlet
and discharge spools where applied stresses can be high. El Segundo has had
several leaks due to carbonate SCC of stress relieved piping, almost all of it around
pumps. The reflux discharge line and de-ethanizer feed discharge line were

upgraded to 316 stainless for that reason. Examples of piping that was upgraded
because of carbonate stress cracking concerns include the piping between the over-
head receiver and product separator at Pascagoula, and a portion of the main frac-
tionator overhead reflux line at Richmond (prior to the Modernization Project).
3290 References
1. Niccolls, E. H. P105 FCC Fractionator Bottoms Pumps: Fabrication Difficul-
ties, Future Metallurgies, Materials Division File 75.16.76, April 15, 1986.
2. Hutchings, I. M. Monograph of the Erosion of Materials by Solid Particle
Impact, Publication No. 10 of The Materials Technology Institute of The
Chemical Process Industries, Inc., 1983.
3. Finnie, I., A. Levy and D. H. McFadden. Fundamental Mechanisms of Erosive
Wear of Ductile Metals by Solid Particles, Erosion: Prevention and Use for
Applications, ASTM STP 664, W. F. Adler, Ed. American Society for Testing
and Materials, 1979, pp. 3658.
4. Cocke, B. J. Hardfacing Erosion Tests in FCC Catalyst, Materials Division
File 95.05.15, March 31, 1986.
5. Informal telephone survey of current hardfacing materials in FCC locations,
telephone notes, Materials Division File 75.16.76, September 8, 1983.
6. Jack, B. L. Examination of Regenerated Catalyst Slide Valves, Irving FCC,
Materials Division File 75.16.76 Irving, March 16, 1983.
7. Moore, D. E. El Segundo FCC Slide Valve Analysis for Ferrite and Sigma
Content, Materials Division File 75.16.76 El Segundo, April 22, 1983.
8. Beck, F. H. Effects of Ferrite and Sensitization on Intergranular and Stress
Corrosion Behavior of Cast Stainless Steels, ASTM STP-610, Stress Corro-
sion New Approaches, pp. 381398.
9. Cantwell, J. E. Caltex Survey of Stainless Steel Slide Valves.
10. Prince, F. C. FCC Regenerated Catalyst U-Bend Slide Valve Bonnet Leak,
Materials Division File 75.16.76, September 6, 1983.
11. Halsted, W. G. High-Temperature Oxidation in Catalytic Cracking Regenera-
tors, Materials Division File 75.16.76, March 8, 1979.
12. Piehl, R. L. Correlation of Hydrogen Sulfide Corrosion at Elevated Tempera-
tures, Materials Division File 18.50, February 23, 1987.
13. Lenhart, S. L. High-Temperature Oxidation Relationship Between Time,
Temperature and Oxide Thickness, Materials Division File 18.45,
August 1, 1979.
14. Lenhart, S. L. Effectiveness of Corrosion Control Programs, FCC Overhead
Gas Recovery Sections, Materials Division 75.16.76, January 29, 1980.

15. French, E. C. Corrosion and H2S Blistering Control in Sour Water Streams,
Materials Performance, March 1978, pp. 2025.
16. Gutzeit, J. Corrosion of Steel by Sulfides and Cyanides in Refinery Conden-
sate Water, Materials Protection, January 1969, pp. 4147.
17. Coombs, J. W. Study of FCC Inner Cooler Corrosion, Status Report, Mate-
rials Division File 75.16.76, January 23, 1973.
18. Informal Survey of Polysulfide Problems and Usage, telephone notes, Mate-
rials Division File 75.16.76, September 9, 1983.
19. Niccolls, E. H. Richmond FCC Fractionator Overhead Corrosion and
Cracking, Materials Division File 75.16.76, December 19, 1985.
20. Skogsberg, J. W. Memo to File, E-140, El Segundo Inner Cooler Corrosion
and Replacement Materials, Materials Division File 75.16.76, May 31, 1983.
21. Telecon, Fred Petterson, Chevron Research Company.
22. Buscemi, C. D. Polysulfide Corrosion Inhibitor Application Guide, Materials
Division File 20.10/18.80.15, September 30, 1988.
23. Moore D. E., and W. E. Erwin Hawaii Fractionator Overhead Condenser and
De-Butanizer Overhead Failures, Materials Division File 75.16.76,
January 5, 1979 and February 29, 1980; and 75.16.56, February 24, 1983.
24. Truax, D. J. FCC Compressor Interstage Coolers E5532A & B -Hawaiian
Refinery, March 17, 1986 and Hawaii Refinery FCC Overhead Exchanger
Corrosion (with brief summary of other FCCUs) March 13, 1986, Materials
Division File 75.16.76.
25. Ehmke, E. F. Polysulfide Stops FCCU Corrosion, Hydrocarbon Processing,
July, 1981, p. 149.
26. Effinger, R. T., M. L. Renquist, A. Wachter, and J. G. Wilson. Hydrogen
Attack in Refinery Equipment, Proc. A.P.I., Vol. 31 M, 1951.
27. National Association of Corrosion Engineers, NACE Standard MR-01-75.
28. Gaertner, D. J. Metallurgical Examination - FCCU 1241 CA-4 Line. Gulf
Research Report File: JT52, January 18, 1984.
29. Merrick, R. D. Refinery Experience with Cracking in Wet H2S Environ-
ments, Corrosion 87, paper #190.
30. Welding Research Council. Graphitization of Steel in Petroleum Refining
Equipment, Bulletin No. 32, New York, NY, January 1957.
31. Thielsch, H., E. M. Phillips, and E. R. Jerome Considerations in the Evalua-
tions of Graphitization in Piping Systems, Welding Journal, June 1955.
32. Shargay, C. A. Cracked Spend Catalyst Line - Port Arthur FCC 1241, Mate-
rials Division File 75.16.76 Port Arthur, June 6, 1985.

33. Semmel, R. A. Validation of Ultrasonic Inspection Technique for Graphitiza-

tion in C-4 Spent Catalyst Return Line - Port Arthur FCCU 1241, Materials
Division File 75.16.76 Port Arthur.
34. Jack, B. L. FCCU Slide Valve and Feed Nozzle Erosion Failures, Richmond,
Materials Division File 75.16.76, April 13, 1984.
35. Shargay, C. A. Ceramic Shroud Liners for FCC Feed Spray Nozzles, Mate-
rials Division File 75.16.76, January 11, 1985.
36. Wilson, L. A. El Paso Refinery FCC Feed Spray Nozzles, El Paso File
313.11(18), June 13, 1985.
37. Shargay, C. A. Memo to File: Failed El Paso FCC Ceramic Spray Nozzle
Insert, Materials Division File 75.16.76, November 1, 1985.
38. Vincent, C. L., S. J. Michael. Memo to File: Failed El Segundo FCC Ceramic
Spray Nozzle Insert, Materials Division File 75.16.76, April 14, 1986.
39. Sedgwick, J. C. Trip Report, Irving Refinery (Radiographic Inspection of FCC
Reactor Feed Nozzles, Richmond Inspection Section, February 21, 1984.
40. Apple, C. H., F. A. Pettersen. X-Ray Monitoring of FCCU Feed Nozzle
Erosion, Transmittal from Chevron Research Company to Caltex Petroleum
Corporation, July 30, 1984.
41. Colombo, M. A. E-1901 C FCC Overhead Condenser, Cracking Unit No. 2,
El Paso, Materials Division File 75.16.76, October 6, 1988.
42. Konet, R. R. Carbonate Stress Corrosion Cracking: Literature Survey,
Chevron ETD memorandum, File 75.16.76, April 18, 1988.
43. Truax D. J., and L. A. Frederickson, FCC Fractionator Overhead Cracking
Meeting, Richmond, May 3, 1988, Chevron ETD memorandum, File 75.16.76,
May 12, 1988.
44. Kmetz, J. H., and D. J. Truax, Carbonate Stress Corrosion Cracking of Carbon
Steel in Refinery FCC Main Fractionator Overhead Systems, presented at
NACE Corrosion/90, April 23-27, 1990.
45. Mezzanatto, J. P. Local Post Weld Heat Treatment Evaluation Final Update,
FCC SCC Memo 040, Pascagoula Refinery memo, Materials Division file
75.16.76, December 6, 1991.
46. Dufault, R.S., FCC Overhead Corrosion Control Guidelines, Materials Engi-
neering file 75.16.76.02, October 28, 1998.

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3200 Fluid Catalytic Cracking Units

Author: R.S. (Scott) DuFault

3210 Introduction 3200-2

Chevron Corporation 3200-1 August 1999

High Temperature Sulfidation

Aqueous Phase Corrosion

August 1999 3200-2 Chevron Corporation

Control Method: Use proper inhibitors or ammonium polysulfide injection and

3211 Process Description

Chevron Corporation 3200-3 August 1999

Reactor and Regenerator

August 1999 3200-4 Chevron Corporation

Flue Gas Section

3220 Catalyst Erosion

Chevron Corporation 3200-5 August 1999

3221 Mechanism of Catalyst Erosion

Properties of the Catalyst

August 1999 3200-6 Chevron Corporation

Chevron Corporation 3200-7 August 1999

August 1999 3200-8 Chevron Corporation

Chevron Corporation 3200-9 August 1999

August 1999 3200-10 Chevron Corporation

Temperature. Data relating the effect of temperature on catalyst erosion is some-

Chevron Corporation 3200-11 August 1999

August 1999 3200-12 Chevron Corporation

approximately 1000F. For hotter locations, Stellite 6 (a cobalt-based hardfacing)

Feed Nozzle Erosion (Equipment Design)

Chevron Corporation 3200-13 August 1999

August 1999 3200-14 Chevron Corporation

Chevron Corporation 3200-15 August 1999

August 1999 3200-16 Chevron Corporation

Richmond developed radiography techniques for monitoring the condition of the

3230 Slide Valve Failures

Chevron Corporation 3200-17 August 1999

Corrosion Prevention and Metallurgy Manual

Mechanical Design Considerations

Union Carbide 80Cr3C2, 20 Rc 48-50 to 17 D-Gun 1800 grindable No Yes all

Watson Grinding 83 WC, Rc 62 to 25 Jetkote 1200 grindable No Yes all

Sermatech 85 WC, 1000 to 20 Gatorgard 1100 grindable No Yes all

Chromizing B diffusion 1600-1900 4-5 CVD 1200 grindable No No Ferrous.

3200 Fluid Catalytic Cracking Units

Corrosion Prevention and Metallurgy Manual

Boroloy B6 Si 2050 to 40 CVD 2075 grindable No No Ferrous,

Boroloy B4 C 2200 to 30 CVD 2075 grindable No No Ferrous,

Turbine Metals carburized + 1700-1900 4-5 CVD 1200 grindable No No Ferrous.

Tech. B. diff. Better on

3200 Fluid Catalytic Cracking Units

Cast Stainless Steel

Wrought (Fabricated) Stainless Steel

Avoiding Slide Valve Problems

August 1999 3200-20 Chevron Corporation

If a steam purge is used, intermittent rather than continuous purging is

3240 Polythionic Acid SCC of Regenerator Internals

3250 Oxidation and Graphitization

Chevron Corporation 3200-21 August 1999

Fig. 3200-11 Effect of Temperature on Oxidation Rate of Steels

August 1999 3200-22 Chevron Corporation

3260 High Temperature Hydrogen Sulfide Corrosion

Chevron Corporation 3200-23 August 1999

3270 Low Temperature Hydrogen Sulfide Corrosion and Associated

3271 Fractionator Overhead Corrosion

August 1999 3200-24 Chevron Corporation

Overhead Hydrogen Sulfide Corrosion Mechanism

Fe Fe++ + 2e- (anodic)